CN119143605A - Recovery method of ethyl acetate and application thereof - Google Patents
Recovery method of ethyl acetate and application thereof Download PDFInfo
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- CN119143605A CN119143605A CN202411287188.2A CN202411287188A CN119143605A CN 119143605 A CN119143605 A CN 119143605A CN 202411287188 A CN202411287188 A CN 202411287188A CN 119143605 A CN119143605 A CN 119143605A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention relates to the technical field of ethyl acetate recovery and provides a recovery method and application of ethyl acetate, wherein the method comprises the steps of adding an acidic aqueous solution into concentrated ethyl acetate generated in the process of extracting activacaine hydrochloride by using ethyl acetate as an organic solvent for pH adjustment, fully stirring, standing and layering to obtain an organic phase I; washing the first organic phase by using purified water, fully stirring, standing and layering to obtain a second organic phase; concentrating the organic phase II to obtain fraction, and collecting recovered ethyl acetate, wherein the recovered ethyl acetate is applied to the extraction process of the atecan hydrochloride, and the extraction effect of the recovered ethyl acetate can reach the extraction effect of new ethyl acetate, so that the reuse rate of the ethyl acetate as an organic solvent can be improved, the waste of ethyl acetate materials is reduced, the waste liquid treatment cost is reduced, and the environmental pollution is reduced.
Description
Technical Field
The invention relates to the technical field of ethyl acetate recovery, in particular to a recovery method of ethyl acetate and application thereof.
Background
The molecular formula of the actecaine hydrochloride is C 13H20N2O3 S & HCl, the molecular weight is 320.8, and the structural formula is as follows:
The atecan block nerve conduction along nerve fibers at an injection position and plays a role in local anesthesia, and compared with other local anesthetics, the atecan has the main characteristics of high anesthetic effect time, high tissue infiltration, no need of blocking anesthesia, high anesthetic efficiency, large safety range, proper anesthesia duration, lower anaphylactic incidence, less influence on cardiovascular systems and low toxic and side effects. Is particularly suitable for surgical procedures involving osteotomies and mucotomy. It is also the only local anesthetic for oral cavity available in domestic market at present.
At present, the preparation method of the atecan hydrochloride mainly comprises a series of operations of acylation, amination, salifying, refining, pulping and drying, and finally 4-methyl-3- [ [ 1-oxo-2- (propylamino) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester hydrochloride, namely the atecan hydrochloride is produced. In the preparation method, a large amount of ethyl acetate is generated in the concentration process of ethyl acetate phase after extraction of an aminated product 4-methyl-3- [ [ 1-oxo-2- (propylamino) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester after amination reaction, but because excessive n-propylamine is added in the preparation process of the 4-methyl-3- [ [ 1-oxo-2- (propylamino) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester, the n-propylamine is easily dissolved in the ethyl acetate, the concentrated ethyl acetate contains n-propylamine and cannot be directly reused, and only can be directly abandoned as a waste solvent, and a large amount of ethyl acetate is required for extracting the aminated 4-methyl-3- [ [ 1-oxo-2- (propylamino) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester, so that great waste is caused by direct treatment as a waste liquid.
Thus, the ethyl acetate generated in the concentration process is treated to be reused for extracting the 4-methyl-3- [ [ 1-oxo-2- (propylamino) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester generated by amination, which is of great significance to the preparation process and environmental protection of the atecan hydrochloride.
Disclosure of Invention
The invention provides a recovery method of ethyl acetate and application thereof, and solves the problem of serious ethyl acetate waste in the related technology.
The technical scheme of the invention is as follows:
In a first aspect, the invention discloses a recovery method of ethyl acetate, comprising the following steps:
s1, adding an acidic aqueous solution into concentrated ethyl acetate generated in the process of extracting the atecrine hydrochloride by using ethyl acetate as an organic solvent to adjust the pH, and standing for layering after fully stirring to obtain an organic phase I;
And S2, washing the organic phase I by using purified water, fully stirring, standing and layering to obtain an organic phase II, concentrating the organic phase II, and collecting fractions to obtain the recovered ethyl acetate.
Further, in step S1, the acidic aqueous solution includes a composition of one or more of hydrochloric acid, phosphoric acid, acetic acid, and sulfuric acid;
Preferably, the acidic aqueous solution is hydrochloric acid.
Further, the concentration of the acidic aqueous solution is 0.1 mol/L to 1 mol/L;
preferably, the concentration of the acidic aqueous solution is 0.1 mol/L.
Further, in step S1, when an acidic aqueous solution is added to perform pH adjustment, the pH value is adjusted to 1-6;
preferably, the pH is adjusted to 4-5.
Further, in step S2, when the first organic phase is washed with purified water, the amount of purified water is 5% -30% of the amount of concentrated ethyl acetate;
Preferably, the purified water is 10% of the concentrated ethyl acetate
Further, in the step S2, the concentration treatment method comprises adopting a decompression vacuum concentration method, wherein the vacuum degree- (0.04-0.10) MPa and the collection temperature are 30-70 ℃;
preferably, the vacuum degree is- (0.08-0.10) MPa, and the collection temperature is 40-50 ℃;
Further, the collection temperature is the feed liquid temperature of the second phase in the process of vacuum concentration under reduced pressure, so that the temperature change can be observed in the production process conveniently.
Further, in the steps S1 and S2, the stirring time is 5min-60min, and the standing time is 5min-60min;
Preferably, the stirring time is 10min-15min, and the standing time is 20min-30min.
Based on this, a preferred ethyl acetate recovery method in the present invention is obtained, specifically as follows:
Adding 0.1 mol/L hydrochloric acid solution into concentrated ethyl acetate generated in the process of extracting the atecan hydrochloride by using ethyl acetate as an organic solvent, adjusting the pH to 4, fully stirring for 10min, standing for 25min, and layering to obtain an organic phase I;
washing the organic phase I by using enough purified water, fully stirring for 10min, standing for 25min for layering to obtain an organic phase II, concentrating the organic phase II by using a reduced pressure vacuum concentration method (vacuum degree-0.08 MPa, collection temperature 45 ℃), and collecting fractions to obtain the recovered ethyl acetate.
In a second aspect, the invention also discloses an application of the ethyl acetate recovery method, and the recovered ethyl acetate is applied to the extraction process of the atecan improve the reuse rate of the ethyl acetate as an organic solvent, reduce the waste of ethyl acetate materials, reduce the waste liquid treatment cost and reduce the environmental pollution.
Further, the procedure of the extraction process of applying the recovered ethyl acetate to the atecan hydrochloride is as follows:
Dissolving 4-methyl-3- [ 1-oxo-2- (chloro) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester in DMF (dimethylformamide), heating to 35 ℃ to +/-2 ℃ for dissolution, starting to dropwise add n-propylamine, controlling the temperature to 35 ℃ to +/-2 ℃, controlling the temperature to 35-40 ℃ after the dropwise addition is finished, carrying out heat preservation reaction for 24 hours, adding recovered ethyl acetate and a prepared saturated aqueous solution of sodium carbonate into the feed liquid after the reaction is finished, stirring for 20 minutes, standing for 30 minutes for layering, and separately collecting an organic phase and a water phase;
Adding the recovered ethyl acetate into the collected water phase again, stirring for 20min, standing for 30min for layering, repeating the step for 1 time, collecting the water phase, and combining the organic phases;
Adding 1.3 times of acetone into the oily matter, stirring and dissolving, controlling the temperature to be less than or equal to 40 ℃, using concentrated hydrochloric acid to adjust the pH value to 5-6, cooling to 0-5 ℃ after the adjustment is finished, preserving heat and crystallizing for 24 hours, filtering, washing a filter cake with a small amount of acetone, adding 2 times of acetone into the obtained solid, heating and refluxing to dissolve the obtained solid, preserving heat for 15 minutes, filtering, cooling the filtrate to 0-5 ℃, preserving heat and crystallizing for 24 hours, filtering, washing the filter cake with a small amount of acetone, repeating the operation for 1 time, and carrying out vacuum drying on the obtained solid to obtain the atercaptan hydrochloride.
The beneficial effects of the invention are as follows:
According to the invention, concentrated ethyl acetate generated in the process of extracting the atecan with ethyl acetate as an organic solvent is recovered, so that recovered ethyl acetate with high recovery rate and purity is obtained, and the recovered ethyl acetate is continuously applied to the extraction process of the atecan with the extraction effect of new ethyl acetate, so that the reuse rate of the ethyl acetate as the organic solvent can be improved, the waste of ethyl acetate materials is reduced, the waste liquid treatment cost is reduced, and the environmental pollution is reduced.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The recovered ethyl acetate was prepared.
Adding 0.1mol/L hydrochloric acid solution into 1kg of concentrated ethyl acetate generated in the process of extracting the atecan hydrochloride by using ethyl acetate as an organic solvent, adjusting the pH to 4, fully stirring for 10min, standing for 25min, and layering to obtain an organic phase I;
Washing the organic phase I by using 100g of purified water, fully stirring for 10min, standing for 25min for layering to obtain an organic phase II, concentrating the organic phase II by using a reduced pressure vacuum concentration method (vacuum degree-0.08 MPa, collection temperature 45 ℃), and collecting fractions to obtain the recovered ethyl acetate.
The mass of the ethyl acetate is 850g, the recovery rate of the ethyl acetate is 85% by calculation, and the purity of the ethyl acetate is 99.9% (the standard content is more than or equal to 99.5%) by detection.
Example 2
The recovered ethyl acetate was prepared.
The preparation process differs from example 1 only in that in step one, 0.1 mol/L of hydrochloric acid solution is replaced by 0.1 mol/L of phosphoric acid aqueous solution, the other conditions being exactly the same, and finally recovered ethyl acetate is obtained.
The mass of the ethyl acetate was 849g, the recovery rate of the ethyl acetate was 84.9% by calculation, and the purity of the ethyl acetate was 99.6% by detection.
Example 3
The recovered ethyl acetate was prepared.
The preparation process differs from example 1 only in that in step one, 0.1 mol/L of hydrochloric acid solution is replaced by 0.1 mol/L of aqueous acetic acid solution, the other conditions being exactly the same, and finally recovered ethyl acetate is obtained.
The mass of the ethyl acetate is 851g, the recovery rate of the ethyl acetate is 85.1% through calculation, and the purity of the ethyl acetate is 99.5% through detection.
Example 4
The recovered ethyl acetate was prepared.
The preparation process differs from example 1 only in that in step one, 0.1 mol/L of hydrochloric acid solution is replaced by 0.1 mol/L of sulfuric acid aqueous solution, the other conditions being exactly the same, and finally recovered ethyl acetate is obtained.
The mass of the ethyl acetate is 850g, the recovery rate of the ethyl acetate is 85% by calculation, and the purity of the ethyl acetate is 99.6% by detection.
The recovery and purity of the recovered ethyl acetate prepared in examples 1-4 are listed in table 1, table 1 as follows:
TABLE 1
| Recovery (%) | Purity (%) (Standard. Gtoreq.99.5%) | |
| Example 1 | 85.0 | 99.9 |
| Example 2 | 84.9 | 99.6 |
| Example 3 | 85.1 | 99.5 |
| Example 4 | 85.0 | 99.6 |
Analysis of the data in table 1 shows that the recovery rate of recovered ethyl acetate obtained by recovering concentrated ethyl acetate produced in the process of extracting the atecan with ethyl acetate as an organic solvent reaches about 85%, the recovery rate is high, the purity reaches 99.5% or more, and the recovery rate meets the standard purity, so that the recovered ethyl acetate can be reused.
Test examples 1 to 4
Extracting the atecan hydrochloride by using ethyl acetate as an organic solvent.
The ethyl acetate recovered in examples 1 to 4 was used as an organic solvent for the extraction of atecrine hydrochloride, respectively, and four groups of tests were performed, each group of which was subjected to the test extraction as follows.
Dissolving 100g of 4-methyl-3- [ 1-oxo-2- (chloro) -propyl ] amino ] -2-thiophenecarboxylic acid methyl ester in 300gDMF ℃, heating to 35 ℃ for dissolution, starting to dropwise add 100mL of n-propylamine, controlling the temperature at 35 ℃ after the dropwise addition is finished, carrying out heat preservation reaction for 24 hours, adding 100g of recovered ethyl acetate and 100g of prepared saturated aqueous solution of sodium carbonate into the feed liquid after the reaction is finished, stirring for 20 minutes, standing for 30 minutes for layering, and separately collecting an organic phase and a water phase;
adding 200g of recovered ethyl acetate into the collected water phase again, stirring for 20min, standing for 30min for layering, repeating the step for 1 time, collecting the water phase, and combining the organic phases;
Adding 1.3 times of acetone into the oily matter, stirring and dissolving, controlling the temperature to be less than or equal to 40 ℃, using concentrated hydrochloric acid to adjust the pH value to 5, cooling to 3 ℃ after the adjustment, preserving heat and crystallizing for 24 hours, filtering, washing a filter cake by 1 time of acetone, adding 2 times of acetone into the solid obtained after washing, preserving heat and refluxing for dissolving clear at 25 ℃ for 15 minutes, filtering, cooling the filtrate to 3 ℃, preserving heat and crystallizing for 24 hours, filtering, washing the filter cake by 1 time of acetone, repeating the operation for 1 time, and vacuum drying the obtained solid at 70 ℃ for 8 hours to finally obtain the atecan hydrochloride.
Comparative example 1
Extracting the atecan hydrochloride by using ethyl acetate as an organic solvent.
The difference from the test example was that the recovered ethyl acetate was replaced with fresh ethyl acetate (ethyl acetate used for the first time after purchase, purity 99.8%) under the same conditions, and atecan be finally obtained.
The yields and purities of the atecrine hydrochloride obtained by extraction of test examples 1 to 4 and comparative example 1 were calculated and examined, and the results are shown in table 2, table 2 below:
TABLE 2
Analysis of the data in Table 2 shows that the yield and purity of the atecan be improved by applying the recovered ethyl acetate obtained by the recovery method of the invention to the extraction process of the atecan, compared with the atecan hydrochloride obtained by the extraction of comparative example 1, the yield and purity of the atecan be improved by the extraction of the atecan obtained by the extraction of test examples 1-4.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2780584A (en) * | 1983-05-09 | 1984-11-15 | Hoechst A.G. | Extractive separation of alcohols and esters |
| JP2007210980A (en) * | 2006-02-13 | 2007-08-23 | Sanwa Yuka Kogyo Kk | Method for recovering ethyl acetate from ethyl acetate/methyl ethyl ketone mixture system |
| CN110483296A (en) * | 2019-09-12 | 2019-11-22 | 新中天环保股份有限公司 | A kind of recovery method of pharmacy class ethyl acetate solvent slop |
| CN111689857A (en) * | 2020-05-18 | 2020-09-22 | 南京工业大学 | Resource utilization method of ethyl acetate production wastewater |
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- 2024-09-13 CN CN202411287188.2A patent/CN119143605B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2780584A (en) * | 1983-05-09 | 1984-11-15 | Hoechst A.G. | Extractive separation of alcohols and esters |
| JP2007210980A (en) * | 2006-02-13 | 2007-08-23 | Sanwa Yuka Kogyo Kk | Method for recovering ethyl acetate from ethyl acetate/methyl ethyl ketone mixture system |
| CN110483296A (en) * | 2019-09-12 | 2019-11-22 | 新中天环保股份有限公司 | A kind of recovery method of pharmacy class ethyl acetate solvent slop |
| CN111689857A (en) * | 2020-05-18 | 2020-09-22 | 南京工业大学 | Resource utilization method of ethyl acetate production wastewater |
Non-Patent Citations (2)
| Title |
|---|
| DRUECKHAMMER, DG, ET AL: "Acetone-Heptane as a Solvent System for Combining Chromatography on Silica Gel with Solvent Recycling", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 1, no. 1, 7 January 2013 (2013-01-07), pages 87 - 90 * |
| 栾国颜: "从废酯液中回收醋酸乙酯的分离技", 现代化工, vol. 03, 20 March 2007 (2007-03-20), pages 44 - 47 * |
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